Unsaturated esters of haloaryloxy alcohols



Patented Nov. 7, 1944 UNSATURAT'ED ESTERS OF HALO- 1 ARYLOXY ALCOHOLS Gerald n. Coleman and Bartholdt c. Hadler, Midland, Mich., assignors to The Dow Chemical Company, Midland, Mich.,

Michigan a corporation of No Drawing. Application September 25, 1941, Serial No. 412,297

' 3 Claims .(Cl. 260-486) This invention concerns esters of halo-aryloxysubstituted lower alcohols with certain unsaturated aliphatic mono-carboxylic acids, said esters having the general formula X 3 o-n'0o -R wherein X represents a halogen substituent, R represents a lower alkylene radical containing from two to six carbon atoms, Rrepresents an aliphatic hydrocarbon radical containing not more than ten carbon atoms and at least one ethylenic linkage, 12 represents the number ofsubstituents on the aryl nucleus and is not greater than 4. All such esters are high-boiling liquids or crystalline solids which are substantially insoluble in water, but are readily soluble in organic solvents. The compounds are useful as plasticizing or modifying agents for vinyl resins, e. g. polystyrene, and cellulosederivative (e. g. ethyl cellulose, cellulose acetate, etc) compositions.

The unsaturated esters of, the present class are conveniently prepared by esterifying a haloaryloxy-substituted alcohol, e. g. beta-(2-chlorophenoxy) -propanol, beta-( 2 chloro phenoxy) ethanol, etc., with an aliphatic mono-carboxylic acid which contains not more than ten carbon atoms and at least one ethylenic linkage in the aliphatic residue, e. g. crotonic acid, acrylic acid,

beta-ethyl-acrylic acid, undecylenic acid, sorbic acid, etc. The reaction may be carried out by heating at a temperature of about 60130 C. a mixture of the aryloxy alcohol with approximately one chemical equivalent of the unsaturated mono-carboxylic acid and a small proportion of an esterification catalyst, e. g. approximately 0.01-0.04 molecular equivalent of a strong acid, such as sulphuric or benzene sulphonic acid. Water is formed in the reaction and, if desired, a water-immiscible organic solvent, such as benzene or toluene, may be added to the reaction mixture for the purpose of promoting distillation and removal of the water during the ,esterification. Upon completion of the reaction, the mixture is treated with suflicient alkali to neutralize any free acid, washed with water, and the ester product is separated and purified by fractional distillation or crystallization.

The following example is illustrative of the preparation of the esters of the present class but i not to be construed aslimiting the invention:

Example A mixtureof 88 grams (0.51 mol) of beta-(2- chloro-phenoxy) -ethanol, 43 grams (0.50 mol) of beta-(Z-bromo-phenoxy) -butanol methacrylic acid, '5 grams of benzene sulphonic acid, and 1 gram of 4-cyclohexyl-phenol was heated at a temperature of approximately -88 C. for 2 hours. The 4-cyclohexyl-phenol was employed for the purpose of inhibiting polymerization. Upon completion of the reaction, the mixture was allowed to cool, dissolved in benzene, and washed with dilute aqueous sodium bicarbonate solution. The benzene was then distilled off and the ester product was purified by fractional distillation under vacuum. There was obtained beta-(2-chloro-phenoxy) -ethyl methacrylate, a white'crystalline solid distilling" at approximately -118 C. under 1 millimeter 1 pressure, melting at approximately 32.5-34 C., and having the formula Other unsaturated halo-aryloxy-alkyl esters of the present class may be prepared by the general method illustrated by the foregoing example. For example, gamma-(2.4-dichloro-phenoxy)- propanol may be reacted with acrylic acid to produce gamma-(2.4-dichloro-phenoxy)-propyl acrylate; beta (2.4.5.6 tetrachloro phenoxy) ethanol with crotonic acid to produce beta- (2.4.5.G-tetra-choloro-phenoxy) -ethyl crotonate with betaethylacrylic acid to produce beta-(2-bromophenoxy) -butyl beta-ethylacrylate; beta-(2.4-dibromo-phenoxy) -ethano1 with tiglic acid to produce beta-(2.4-dibromo-phenoxy)-ethyl tiglate; etc.-

This application is a continuation-in-part of our co-pending application Serial No. 371,592, filed December 24, 1940; which is a continuationin-part of our co-pending application Serial No. 321,314, filed February 28, 1940; which, in turn, is a continuation-in-part of application Serial No. 177,655; filed December 1, 1937.

2:1 An ester of a halo-arloxy-substituted lower alcohol and an unsaturated aliphatic mono-carboxylic acid, said ester having the general formula v wherein R represents a lower alkylene radical containing from two to six carbon atoms, R represents an aliphatic hydrocarbon radical containing not more than ten carbon atoms and a single ethylenic linkage, and n represents an inwherein R represents an aliphatic hydrocarbon 'teger not greater than 4. radical containing not more than ten carbon 2. An ester of a chloro-aryloxy-substituted atoms and a single ethylenic linkage. ethyl alcohol and an unsaturated aliphatic mono- 3. Beta-(2-ch1oro phenoxy) ethyl methacrycarboxylic acid, said ester having the general 5 late.

formula GERALD H. COLEMAN.

BARTHOLDT C. HADLER. 

